- alkylmercaptq - benzothiazolie



Patented Nov. 11, 1952 t 2 n ALKYLMERCAPTO BENZ O'LH zp h DERIVATIVES, NPROCESS F PRE- PARING THE SAME Albert Sander, Essen, Germany, ass'ignorto The Goldschmid-t,-A--. Ga, Essen, Ger-manna Germain bodyccrporateNon'r m' Application soptemborls, rota-so: name. 115,568; InGormanyoototen,194s

Glaims2 (01. 260-306) It has been foundthatccmpounds'having valw and areexcellently suited foruse for economic able capillary-active propertieswhich are excelpickling; Contrary to all exp ctations; it has lentl'ysuitable for use as detergents, emulsifiers; been found thatthe1dptirh-um'-efiects* dispersing agents, roaming agents and wettingtiesarepbtaiIied witlrstraiglitor br ncl'i agents, and can be er'nployedto particular ad- 5 phati'c" hydrocarbon chains; are tale'nce" vantagefor economic pickling, are obtained if chain of whichcon'taihsonlyfiftd-fi C=atoms- Z-Ine'rcapto-arylene-thiazole sulphon'ic acids orThe subsequent introduction of the" sulp 6 Z-mercapto-arylene-thiazolecarboxylic acids in group, for example by: treatment with blo neutral orweakly alkaline solution, if necessary sulphonation agents; inwhieht es'ulp'lio group with an addition of: suitable" solvents, are con- 10also entersthe aromatienuoieusagivos ceasefire densed with aliphatic,hydroaromatio o'ri'lnixed' I'S'llllI, S'Ot'h'ali theprbces'is'acodrdirig'toth ifivfialiphatic and aromatic halogencompounds; the" ti'ori' can' alsdb'e carridoutby firstoona hydrocarbonchain of which contains at least 5' alkali salts of thez-mercapto-arylene thiahbles C-atoms. Preferably, organic halogencominstead of the 2-mercapto arylene thiazole sulpounds may beemployedfor the condensation, phonic acids, and subsequently sulphona-ting thewhich have branched hydrocarbon chains whose condensationproducts-obtained. I I main valence chain consists of at least 5C-atoms. The surprising. discovery has also been made It haslong beenknown from technical literat at" hese favourable gene al properties of 75116 ture that aliphatic hydrocarbons are given surcompounds obtainableinaccordance with theinfa e afctive,properties by int ducin hydrophilicvention are substantially due:- to the mercapt o or solubilising groupseither directly orv via suitgroup of the benzothiazole molecule, sinceifltheable bridge linkages. Detergents or other auxilsulphur bridge isreplaced by other atoms or atom iary agents Which can be used inpractice, howps, p i wgen or by t e sulever, are-insuch cases onlyobtained from those phone residue, the pr pertiesofi the condensationaliphatic compounds whose hydrocarbon chain products change in'anunfavour-able-rr z tiin'eie ,ark]v consistsot at least 12 C-atomse Thisis so, for in particular the water solubility thereofdeexample,in-thecase of the-classic detergentsi. e. creases sharply, sothattheyare practicallyusethe soaps, or in the case of the modernpurely less aswashing agents. e H synthetic washing agents, such for example of Theprocess provided by the presentinventi the laur-yl sulphonates, themersolates (alkanethe effects of Whichy 0; means be foresulphonatedetergents prepared by sulphochlori- Seen fIOm the existing nowledge;consequently nation of paraflin hydrocarbons), the ultravonsconstitutes; atechnically and economically very(alkyl-benzimidazolesulphonic acids), igepons Valuable advance, sincevitislthereby possiblent oo (alkane sulphonic acids with amide or esterlinkconvert lower aliphatic compounds which hitherages between thehydrophobic and sulphonic 170 Gould 1101?; Couldionlwtwwlimited;extentsgroups). and others, which all contain'from 12 be put manypracticaluseasiby-products of the to 18 or more C-atoms in theirhydrophobici'part. synthesis of. benzine or, fattyacids; into valuableIfaromatic sulphonic acids-are joinedto aliphatic articles of use.residuesthrough any intermediate links, the compounds obtained quitegenerally exhiibt unsatis- 40 H 4 factory resistance to lime and inaddition usually Parts d l h uIn-2mercapto havedeficient watersolubility, so that washing benzothlazole-fisulphonate s ii aagentswhich are of practical use can only be c sed v ssel providedwithea t i n' obtained by introducing a number of sulpho or m 600-800v s f 7-%;-80% q oh lo.

other solubilising. groups. and dually. mixed ith 80 par by w htv of! Incontrast thereto, it has surprisingly been 9 -00tane"vv1thm11d: boi1i'neCondensafound in accordance with the present invention t earned! out Wmild"2 i nd that precisely th introduction of shorter aliphaticWithTefiuXcoolingifor: 0 hours until the con hains whi h according topreviou experience version is complete. After; the a-loohol' ands thegive nouseful detergent at all, t the Starting excesschloro -dctarrehavebeen-driven 01f", which substances mentioned at the outset gives commaythod, 200 220 parts= pounds having excellent detergent properties, by tOi the' sodiumsalt? of 2-'II'-o'oty mer-' which at the same time haveexcellent resistance p -benzothiazoles t-sulphonici' acid with ato-lim'e, solubility; foaming powenwetting and Sodium GFHQiTidEcommittal? iii d cleansing capacity and: emulsifying properties, onevaporation of the residual solution in analmost theoretical yield, as awhite powder readily soluble in warm water and having an excellentwashing, wetting and foaming ction.

If, in this example, the l-chloro-octane is replaced by 2-chloro-octaneor mixtures of isomeric monochloro-octanes, more readily solubleproducts having similar excellent general properties are obtained.Halogenated hydrocarbons having a branched chain, for exampleZ-ethyll-chloro-hexane, also give readily soluble products havingexcellent washing, wetting and foaming action. The products obtained areremarkable for their excellent resistance to the waterhardening agentsand to acids and retain their surface-active properties both in thealkaline and in the acid zone. Due to the fact that they also haveexcellent stability in strongly acid solution, they are excellentlysuitable as auxiliary carbonising agents.

Example II If, in Example II, the 2-meroaptobenzothiazole-5-sulphonateis replaced by 130 parts by weight of the disodium salts ofZ-mercaptobenzothiazole-5-carboxylic acid, a readily soluble end productsimilar to soft soap and having remarkably favourable detergentproper-ties is obtained in very good yield.

Example IV 140 parts by weight of the acid zinc salt ofZ-mercaptobenzo-thiazole-6-sulphonic acid are suspended in 600-800 partsof alcohol with 200-300 parts of water and mixed with such a quantity of45% soda lye that the zinc is redissolved as zincate. Condensation isthen carried out in the manner described in Example I with 80 parts byweight of 2-chloro-octane, and after the reaction is complete thealcohol is distilled, whereafter the residue of the chloro-octane isdriven off by steam distillation. The distillation residue, from whichthe difficultly soluble zinc salt of the2-octyl-mercaptobenzothiazole-6- sulphonic acid has precipitated as awhite soaplike mass, is brought into solution by acidulation with dilutehydrochloric acid. The zinc is precipitated in the boiling conditionwith hot soda solution as basic zinc carbonate, and after filtering, thehot filtrate is mixed with an equal volume of saturated sodium chloridesolution. The sodium salt of 2(2octyl-)-meroapto-benzothiazole-6-sulphonic acid is thus separated in the formof white soap-like crystal scales, which are filtered oif after cooling.The odourless product is readily soluble in water, has high foaming andwetting capacity and excellent cleansing power. Highly dilute solutionsthereof and those of the isomers render metal surfaces remarkablypassive to acids and are therefore excellently suited for use asadditions to economic pickling agents.

When, for example, a bright sheet-iron strip of 140 g. in weight wassubjected to the action of hot dilute sulphuric acid having a H2504content of 7.5% at C., the reduction in weight after period of action of4 hours amounted to 7.1575 g. but when 0.05% of the sodium salt of2octyl-mercaptobenzothiazole-6-sulphonic acid was added to the sameacid, only 0.0480 g. of metal was dissolved under the same conditions.The ratio of the increase in passivity is therefore 1:149.

Highly rusted sheet-iron specimens were treated for 40 minutes with 500cc. of 5% hydrochloric acid at 80 C. When no passivity-increasing agentswere added, the brisk evolution of gas continued with considerablecorrosion even after the layer of rust had been removed. On the otherhand, when in a parallel experiment about 0.1% of the capillary-activecompounds produced in accordance with the examples of the invention wasadded, the evolution of gas ceased immediately after the layer of rusthad been removed and there remained a bright metal surface without anyvisible traces of corrosion. The reduction in the weight of the specimenamounted in this case only to one-half of that of the sheet metaltreated without the passivity-increasing agent (1.0962 g. as comparedwith 2.0953 g.) and was thus practically equal to the quantity of rustdissolved.

Rusted-in screws can readily be loosened within a short time if treatedwith a few drops of dilute hydrochloric acid containing about 01-05% ofthe products of condensation described in the foregoing examples.

Example V parts of weight of 2-octylmercapto-benzothiazole produced inthe known manner by condensation of the sodium salt ofZ-mercapto-benzothiazole in alcoholic solution with chloro-octane, areintroduced into 300 parts of 25% oleum with cooling, and sulphonated, ifnecessary with heating to about C., until a water-soluble specimen isobtained. The sulphonation mixture is then poured into 2000 parts ofwater and limed out with milk of lime in the hot state and the heavyalkaline solution is separated from the precipitated gypsum byfiltration. After the conversion of the filtrate with a soda solutionand separation of the calcium carbonate thus precipitated, the productis evaporated to dryness and the sodium salt'of2-octylmercaptobenzothiazole sulphonic acid, having similar propertiesto the product obtained in accordance with Example I, is obtained.

Eazample VI 30 parts by weight ofdisodium-Z-mercaptobenzothiazole-6-sulphonate are condensed in themanner described in Example I with 20 parts by weight of pinenehydrochloride. On working up of the reaction mixture the sodium salt of2- bornyl-mercaptobenzothiazo1e-6-su1phonic acid is obtained in goodyield in the form of a white, very readily water-soluble powder. As aderivative of a methylated cyclohexane, it corresponds in itscolloid-chemical behaviour to the corresponding limit hydrocarbonderivatives. A notable feature in this case, however, is the extremelygreat increase in water solubility.

I claim:

1. A capillary active substance of the general formula wherein R is abenzothiazole nucleus, y is a solubilizmg group selected from the groupconsistis an alkyl radical containing 6 to 8 carbon atoms.

3. A capillary active substance in accordance with claim 1, in which thehydrophobic radical a: is a branch chain alkyl radical, the main valencechain of which contains at least 5 carbon atoms.

4. A capillary active substance of the formula Cation 03$ wherein X isan alkyl radical containing 6 to 8 carbon atoms.

5. A process for the preparation of a capillary active substance whichcomprises condensing a compound selected from the group consisting ofZ-mercapto arylene thiazole carboxylic acids and Z-mercapto arylenethiazole sulfonic acids in a neutral to weakly alkaline solution with ahalogenated compound selected from the group consisting of alkyl halidescontaining at least 5 carbon atoms and pinene hydrohalides.

ALBERT SANDER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,750,651 Vignos Mar. 18, 19301,987,526 Elbel Jan. 8, 1935

1. A CAPILLARY ACTIVE SUBSTANCE OF THE GENERAL FORMULA 